Correlation between the molecular structures and thermodynamic parameters of chiral recognition on Host-Guest complexation

主客体络合手性识别的分子结构与热力学参数的相关性

• 批准号: 12640518
• 负责人: HIROSE Keiji
• 金额: $ 1.86万
• 依托单位: OSAKA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640518/
• 关键词: Chiral Recognition; Crown Ether; Amine; Optically Active; Enthalpy; Entropy; Temperature Dependence; Criteria Of Molecular Design

In the cases of many complexations of crown ethers with amines, there is a linear relationship between 1n K and 1/T, which is called the van't Hoff relationship. Based on the van't Hoff relationship, the enthalpy and the entropy can be obtained quantitatively. In addition to an ordinary adopted molecular design based on qualitative host-guest complimentarity judged by a steric hindrance and a fittability between the size of cavity and that of substrate, novel criteria based on the enthalpy and entropy were thought to be contribute to create the precise molecular design of host. Here I extended this idea to a chiral recognition phenomena. I carried out this research as following three steps.(1) The syntheses of optically active artificial hosts and guests, which are correlated by the structural similarity.(2) Measurements of binding constants in the complexation between series of hosts and chiral amines.(3) Investigation of molecular recognition mechanism thinking the thermodynamic parameters.Novel six hosts and both enantiomers of 3 chiral amines were prepared, the measurements of binding constants in the complexation between part of the host-guest combinations were carried out. And the results are published under the consideration of thermodynamic parameters.

在许多冠状醚与胺的络合物的情况下，1N K和1/T之间存在线性关系，这称为Van't Hoff关系。基于Van't Hoff的关系，可以定量获得焓和熵。除了基于定性宿主 - 阵线的普通分子设计外，还以空间的阻碍和腔体大小和底物的拟合性来判断，基于焓和熵的新标准也被认为是有助于创造宿主的精确分子设计的新标准。在这里，我将这个想法扩展到了手性识别现象。我进行了这项研究，如以下三个步骤。（1）光学活跃的人造宿主和客人的合成，它们与结构相似性相关。（2）在宿主和手性胺之间的络合中的结合常数测量。（3）分子识别机制的研究特定动力学的研究均应供应剂和热力学参数。进行了一部分宿主 - 阵线组合之间络合中结合常数的测量。结果在热力学参数的考虑下发表。

项目成果

Keiji Hirose, Kazuko Ogasahara, Kazuyuki Nishioka, Yoshito Tobe, and Koichiro Naemura: "Enantioselective complexation of phenolic crown ethers with chiral aminoethanol derivatives : effects of substituents of aromatic rings of hosts and guests on complexa

Keiji Hirose、Kazuko Ogasahara、Kazuyuki Nishioka、Yoshito Tobe 和 Koichiro Naemura：“酚冠醚与手性氨基乙醇衍生物的对映选择性络合：主体和客体芳环取代基对络合物的影响

Keiji Hirose, Kazuko Ogasahara, Kazuyuki Nishioka, Yoshito Tobe, Koichiro Naemura: "Enantioselective complexation of phenolic crown ethers with chiral aminoethanol derivatives : effects of substituents of aromatic rings of hosts and guests on comoplexatio

Keiji Hirose、Kazuko Ogasahara、Kazuyuki Nishioka、Yoshito Tobe、Koichiro Naemura：“酚类冠醚与手性氨基乙醇衍生物的对映选择性络合：主体和客体芳环取代基对络合的影响

Masami Sawada, Kouji Hagita, Hiroyuki Imamura, Hiroyuki Tabuchi, Shinya Yodoya, Maki Umeda, Yoshio Takai, Hitoshi Yamada, Hiroshi Yamaoka, Keiji Hirose, Yoshito Tobe, Toshikazu Tanaka, Shigetoshi Takahashi: "Chiral Recognition Ability of Crown Ethers towa

Masami Sawada、Kouji Hagita、Hiroyuki Imamura、Hiroyuki Tabuchi、Shinya Yodoya、Maki Umeda、Yoshio Takai、Hitoshi Yamada、Hiroshi Yamaoka、Keiji Hirose、Yoshito Tobe、Toshikazu Tanaka、Shigetoshi Takahashi：“冠醚的手性识别能力 towa

Keiji Hirose, Hiroyuki Naka, Masashi Yano, Sozaburo Ohashi, Koichiro Naemura and Yoshito Tobe: "Improvement of enantioselectivity in kinetic resolution of a primary alcohol through lipase-catalyzed transesterification by using a chiral acyl donor"Tetrahed

Keiji Hirose、Hiroyuki Naka、Masashi Yano、Sozaburo Ohashi、Koichiro Naemura 和 Yoshito Tobe：“使用手性酰基供体通过脂肪酶催化的酯交换反应提高伯醇动力学拆分的对映选择性”

Hirose K.: "A practical guide for the determination of binding constants"J. Incl. Phenom. and Macrocyclic Chem.. 39. 193-209 (2001)

Hirose K.：“测定结合常数的实用指南”J.